Highly Stereoselective Three-Component Reactions of

A Novel Multicomponent Reaction of Arynes, β-Keto Sulfones, and Michael-Type ... Three-component coupling of acetylenic sulfones, Grignard reagents a...
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Highly Stereoselective Three-Component Reactions of Phenylselenomagnesium Bromide, Acetylenic Sulfones, and Saturated Aldehydes/Ketones or r,β-Unsaturated Enals or Enones Xian Huang*,†,‡ and Meihua Xie† Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou, 310028, P. R. China, and State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, P. R. China [email protected] Received July 27, 2002

β-Phenylseleno-R-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or R,β-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of R,β-unsaturated enones, functionalized allylic alcohols or functionalized γ,δ-unsaturated ketones were obtained, depending on the structures of the ketones. Introduction

SCHEME 1

Stereodefined vinyl sulfones are important synthetic intermediates due to the presence of the carbon-carbon double bonds and the carbon-sulfur bonds.1 We have shown that the hydrozirconation and hydrotelluration of 1-alkynyl sulfones afforded stereodefined 1-alkenyl sulfones (Scheme 1).2,3 Organomagnesium reagents4 and organic selenides5 are important reagents in organic chemistry and have been extensively studied. However, there are only limited reports on the reaction of magnesium selenolate.6 Back and co-workers have reported that β-(phenylseleno)vinyl sulfones can be synthesized from the selenosulfonation of alkynes or the addition of organocopper reagents to 1-phenylseleno-2-(p-tolylsulfonyl)ethyne.7 On the basis of our results (Scheme 1), we are interested in the selenomagnesiation of 1-alkynyl sulfones leading to 1-alkenyl

SCHEME 2

†

Zhejiang University. Chinese Academy of Sciences. (1) (a) Simpkins, N. S. Sulfones in Organic Synthesis; Pergamon Press: Oxford, 1993. (b) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903. (c) Simpkin, N. S. Tetrahedron 1990, 46, 6951. (d) Na´Jera, C.; Yus, M. Tetrahedron 1999, 55, 10547. (2) Huang, X.; Duan, D. H. J. Chem. Soc., Chem. Commun. 1999, 1741. (3) Huang, X.; Liang, C. G.; Xu, Q.; He, Q. W. J. Org. Chem. 2001, 66, 74. (4) (a) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (b) Thibonnet, J.; Knochel, P. Tetrahedron Lett. 2000, 41, 3319. (5) Commasseto, J. V.; Ling, L. W.; Petragnani, N.; Stefani, H. A. Synthesis 1997, 373. (6) (a) Kamimura, A.; Mitsudera, H.; Asano, S.; Kakehi, A. J. Org. Chem. 1999, 64, 6353. (b) Mitsudera, H.; Kakehi, A.; Kamimura, A. Tetrahedron Lett. 1990, 40, 7389. (c) Kametani, T.; Aizawa, M.; Kurobe, H.; Matsuura, T. Chem. Pharm. Bull. 1982, 30, 1493. (d) Bury, A.; Joag, S. D.; Stirling, C. J. M. J. Chem. Soc., Chem. Commun. 1986, 124. (7) (a) Back, T. G.; Bethell, R. J.; Parvez, M.; Wehrli, D. J. Org. Chem. 1998, 63, 7908. (b) Back, T. G., Collins S., Kerr, R. G. J. Org. Chem. 1983, 48, 3077. ‡

sulfones with an extra Se-containing functional group and a C-Mg bond, providing that the issues of regio- and stereoselectivity can be addressed (Scheme 2). In a preliminary communication, we have observed that the three-component reaction of acetylenic sulfones, phenylselenomagnesium bromide, and aldehydes afforded β-(phenylseleno)vinyl sulfones with high stereoselectivity.8 In this paper, we wish to report the threecomponent reaction of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or R,β-unsaturated enals or enones in detail. Results and Discussion Two-Component Reaction of Phenylselenomagnesium Bromide and 1-Phenyl-2-(p-tolylsulfonyl)ethyne. We first investigated the conjugate addition of phenylselenomagnesium bromide to 1-phenyl-2-(p-tolylsulfonyl)ethyne. At -20 °C, when 1-phenyl-2-(p-tolylsulfonyl)ethyne (1a) was added to the THF solution of phenylselenomagnesium bromide (2) and stirred for 5 (8) Huang, X.; Xie, M. H. Org. Lett. 2002, 4, 1331.

10.1021/jo026249b CCC: $22.00 © 2002 American Chemical Society

Published on Web 11/08/2002

J. Org. Chem. 2002, 67, 8895-8900

8895

Huang and Xie TABLE 1. Reaction of Phenylselenomagnesium

TABLE 2. Conjugate Addition of

Bromide with 1-Phenyl-2-(p-tolylsulfonyl)ethynea

1-Phenyl-2-(p-Tolylsulfonyl)ethyne, Phenylselenomagnesium Bromide and p-Chlorobenzaldehydea

entry

solvent

time (min)

yield (%)b

ratio of Z/Eb

1 2 3 4 5 6

THF THF/CH2Cl2 THF/CH2Cl2 THF/CH2Cl2 THF/CH2Cl2 THF/CH2Cl2

5 5 10 20 30 40

70 76 72 70 70 68

2/1 3/1 2.2/1 1.5/1 1.3/1 1.1/1

The reaction was carried out at -20 °C using 1a (0.5 mmol) and 2 (0.6 mmol). b Determined by 400 MHz 1H NMR analysis of the crude reaction mixture. a

min followed by protonolysis, the expected product, 1-phenyl-1-phenylseleno-2-(p-tolylsulfonyl)ethene 4, was obtained in 70% yield with a ratio of Z/E ) 2/1 (entry 1, Table 1). When the reaction was carried out in THF/CH2Cl2 (v/v ) 1/4), the stereoselectivity was better (the ratio of Z/E ) 3/1) (entry 2, Table 1). The ratio of Z/E decreased with prolonged reaction time (entries 3-6, Table 1). Z-4 was a known compound; however, the 1H NMR data observed here are quite different from what was published in the literature.7a Thus, the structure of Z-4 was further established unambiguously by an X-ray diffraction study.9 The structure of E-4 was characterized by 1H NMR spectral data, which is identical to what was published in the literature.7b Stereoselective Three-Component Reaction of Phenylselenomagnesium Bromide, Acetylenic Sulfones, and Aldehydes. When p-chlorobenzaldehyde (5c) was added to the solution of 1-phenyl-2-(p-tolylsulfonyl)ethyne (1a) and magnesium selenolate (2) at -20 °C in THF/CH2Cl2 (which had been stirred for 10 min) and stirred for 60 min, the adduct 3-phenyl-3-phenylseleno2-(p-tolylsulfonyl)-1-(p-chlorophenyl)-2-propen-1-ol (6c) was formed in 75% yield with a Z/E ratio of 2.7/1 (entry 1, Table 2). With prolonged reaction time for mixing 1a and the magnesium selenolate 2, the ratio of Z/E dropped (entries 2-4, Table 2). When p-chlorobenzaldehyde (5c) was added directly to the solution of phenylselenomagnesium bromide in THF/ CH2Cl2 at -20 °C with stirring for 3 h, the corresponding 1,2-addition product 7 was not detected in the 1H NMR spectrum of the crude reaction mixture. p-Chlorobenzaldehyde (5c) was recovered in 82% yield and diphenyl diselenide was obtained in 95% yield (Scheme 3). The results show that phenylselenomagnesium bromide (2) can react with 1-phenyl-2-(p-tolylsulfonyl)ethyne (1a) preferably to form the vinylmagnesium intermediate in (9) Crystal data for Z-4: C21H18O2SSe, MW ) 413.37, monoclinic, space group P21/n, a ) 12.574(4) Å, b ) 12.087(3) Å, c ) 13.132(5) Å; R ) 90°, β ) 107.973(4)°, γ ) 90°. V ) 1898.5(9) Å3, T ) 293 K, Z ) 4, Dc ) 1.446 g cm-1, µ ) 2.098 mm-1, λ ) 0.71073 Å; F(000) 840, 3351 independent reflections (Rint ) 0.0380), 7684 reflections collected; refinement method, full-matrix least-squares on F2; goodness-of-fit on F2 )1.012; final R indices [I > 2σ(I)] R1 ) 0.0484, wR2 ) 0.1085.

8896 J. Org. Chem., Vol. 67, No. 25, 2002

entry

time (min)

yield of 6c (%)b

ratio of Z/Eb

1 2 3 4

10 20 30 50

75 70 65 65

2.7/1 1.5/1 1.4/1 1/1

a The reaction was carried out at -20 °C using 1a (0.5 mmol), 2 (0.6 mmol) and 5c (0.5 mmol). b Determined by 400 MHz 1H NMR spectra.

SCHEME 3

SCHEME 4

the one-pot reaction of 1a, 2, and 5c. So it is possible for 5c to capture the vinylmagnesium intermediate 3 immediately in hope of improving the stereoselectivity. In fact, it is interesting to note that 3-phenyl-3phenylseleno-2-(p-tolylsulfonyl)-1-(p-chlorophenyl)-2-propen-1-ol (6c) was afforded in 77% yield with a Z/E ratio of 88/12 when 1-phenyl-2-(p-tolylsulfonyl)ethyne (1a) and p-chlorobenzaldehyde (5c) were added simultaneously to the solution of phenylselenomagnesium bromide (2) in THF. Furthermore, with the addition of CH2Cl2 as the cosolvent, the reaction at -20 °C afforded 6c in 82% yield with a Z/E ratio as high as >96/4 (Scheme 4), indicating a dramatic solvent effect. Further studies showed that the reaction is general for differently substituted acetylenic sulfones and aldehydes: R1 can be an alkyl (entries 2, 4, 5, 7, 8, 10, 11,

Three-Component Conjugate-Nucleophilic Addition TABLE 3. Three-Component Reaction of Acetylenic Sulfones with Phenylselenomagnesium Bromide and Aldehydesa

entry

R1

R2

time (min)

yield of Z-6 (%) (Z/E)b

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Ph n-C5H11 Ph n-C4H9 n-C5H11 Ph n-C4H9 n-C5H11 Ph n-C4H9 n-C5H11 Ph n-C4H9 n-C5H11 Ph n-C5H11 n-C4H9 n-C5H11 Ph Ph

p-NO2C6H4 p-NO2C6H4 p-ClC6H4 p-ClC6H4 p-ClC6H4 Ph Ph Ph p-CH3OC6H4 p-Me2NC6H4 p-CH3OC6H4 2-furyl 2-furyl 2-furyl n-C4H9 n-C4H9 styryl styryl vinyl propenyl

50 50 50 70 60 50 60 60 55 50 70 80 80 80 75 70 90 90 70 70

80 (6a, >96/4) 78 (6b, >96/4) 82 (6c, >96/4) 82 (6d, >99/1) 83 (6e, >98/2) 76 (6f, >98/2) 82 (6g, >98/2) 88 (6h, >98/2) 84 (6i, >98/2) 76 (6j, >99/1) 73 (6k, >99/1) 89 (6l, >97/3) 85 (6m, >99/1) 89 (6n, >96/4) 85 (6o, >97/3) 76 (6p, >97/3) 74 (6q, >97/3) 88 (6r, >96/4) 60 (6s, >96/4) 75 (6t, >96/4)

a The reaction was carried out at -20 °C by adding 1 (0.5 mmol), 2 (0.6 mmol), and 5 (0.5 mmol) simultaneously in THF/CH2Cl2 (v/v )1/4). b Isolated yield of purified Z-6 based on 1. The ratio of Z/E was determined by 400 MHz 1H NMR spectra of the unpurified reaction mixture.

13, 14, and 16-18, Table 3) or phenyl group (entries 1, 3, 6, 9, 12, 15, 19, and 20, Table 3); R2 can be aryl (entries 1-11, Table 3), heteroaryl (entries 12-14, Table 3), and alkyl groups (entries 15 and 16, Table 3). Furthermore, it was interesting to note that even with 2-enals, the reaction occurred highly chemoselectively in a 1,2-addition manner (entries 17-20, Table 3). The structures of these compounds were affirmatively characterized via 1H NMR spectra and the NOESY experiment of Z-6e and the X-ray diffraction analysis of Z-6f.10 Stereoselective Three-Component Reaction of Acetylenic Sulfones, Phenylselenomagnesium Bromide, and Ketones. When 1-phenyl-2-(p-tolylsulfonyl)ethyne (1a) and 2-pentanone (8a) were added simultaneously to the solution of phenylselenomagnesium bromide in THF/CH2Cl2, the 1,2-addition product (Z)-3-methyl-2(p-tolylsulfonyl)-1-phenyl-1-phenylseleno-1-hexen-3-ol (Z9a) was obtained in 70% yield with a high stereoselectivity (Z/E > 95/5). The reaction can be extended to other aliphatic ketones, such as 2-butanone and cyclohexanone. With alkyl-substituted acetylenic sulfone, similar results were observed. The results are summarized in Table 4. However, when aliphatic ketones were replaced by acetophenone, the expected three-component reaction did (10) Crystal data for Z-6f: C28H24O3SSe, MW ) 519.49, monoclinic, space group P21/n, a ) 7.0710(4) Å, b ) 14.6604(9) Å, c ) 24.3432(5) Å; R ) 90°, β ) 94.7550(10)°, γ ) 90°. V ) 2514.8(3) Å3, T ) 293 K, Z ) 4, Dc ) 1.372 g cm-1, µ ) 1.603 mm-1, λ ) 0.71073 Å; F (000) 1064, 4688 independent reflections (Rint ) 0.0754), 13 113 reflections collected; refinement method, full-matrix least-squares on F2; goodnessof-fit on F2 ) 0.657; final R indices [I > 2σ(I)] R1 ) 0.0371, wR2 ) 0.0499.

not occur and compound 1-phenyl-1-phenylseleno-2-(ptolylsulfonyl)ethene (4) was formed surprisingly in 75% yield as the single Z isomer together with 3-hydroxy-1,3diphenyl-1-butanone. 3-Hydroxy-1,3-diphenyl-1-butanone was formed by the self-condensation of acetophenone due to the steric hindrance of the phenyl group (see also the results in Table 6). Acetophenone was acting as an in situ proton source to generate Z-1-phenyl-1-phenylseleno2-(p-tolylsulfonyl)ethene (Z-4) and the magnesium enolate intermediate 10, which further reacted with acetophenone, leading to 3-hydroxy-1,3-diphenyl-1-butanone (Scheme 5). The corresponding reaction with R,β-unsaturated ketone depends on the steric effect around the carbonyl group. The reaction of R,β-unsaturated aliphatic enones gave 1,2-adductsssubstituted allyl alcohols Z-12sstereoselectively,11 while the reaction of R,β-unsaturated aromatic enones gave 1,4-adductsssubstituted γ,δunsaturated ketones Z-14sstereoselectively12 (determined from the 1H NMR spectra of the crude reaction mixture). The results are summarized in Tables 5 and 6, respectively. Compared with aldehydes, the reactions of ketones were slower to afford adducts in lower yields. In these cases, small amounts of 1-phenyl-1-phenylseleno-2-(p-tolylsulfonyl)ethene (4) (8-12%) and the unreacted ketones (5-10%) were detected. Conclusion In conclusion, we have demonstrated that the threecomponent reaction of phenylselenomagnesium bromide, acetylenic sulfones, and carbonyl compounds afforded polysubstituted alkenes in high stereoselectivity. Further studies on the application of the reaction are now in progress in our laboratory.

Experimental Section General Techniques. All the solid products were recrystallized from ethyl acetate and hexanes, and the melting points are uncorrected. All reactions were carried out under a nitrogen atmosphere. THF was distilled from sodium/benzophenone. CH2Cl2 was distilled from calcium hydride; 1H NMR spectra were measured at 400 MHz and all 13C NMR spectra were measured at 100 or 125 MHz in CDCl3 with TMS as the internal standard. Acetylenic sulfones13 and R,βunsaturated ketones14 were prepared by literature methods. The Two-Component Reaction of Phenylselenomagnesium Bromide with Acetylenic Sulfones. Preparation of 4. To a colorless solution of phenylselenomagnesium bromide (0.6 mmol) in THF/CH2Cl2 (v/v ) 1:4, 5 mL) was added acetylenic sulfone (0.5 mmol) at -20 °C with stirring. The reaction mixture was stirred at -20 °C for a given time. Then the reaction was quenched with saturated NH4Cl and extracted with CH2Cl2. The organic phase was washed with saturated brine and dried over MgSO4. After filtration and (11) For the synthesis of substituted allyl alcohols, see: Havra´nek, M.; Dvor _a´k, D. J. Org. Chem. 2002, 67, 2125 and references therein. (12) (a) For the Michael addition of 1-alkenylmetallic reagents with R,β-unsaturated ketones, see: Satoh, Y.; Serizawa, H.; Hara, S.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 5225 and references therein. (b) For metal-catalyzed Claisen rearrangement of allylic ether, see: Higashino, T.; Saleaguchi, S.; Ishii, Y. Org. Lett. 2000, 2, 4193; Renter, J. M.; Salomon, R. G. J. Org. Chem. 1977, 42, 3360. (13) Truce, W. E.; Wolf, G. C. J. Org. Chem. 1971, 36, 1727. (14) (a) Gilman, H. Organic Synthesis, 2nd ed.; Queen’s College: Flushing, NY, 1956; Collect Vol. I, p 77. (b) Mariella, R. P.; Raube, R. R. J. Am. Chem. Soc. 1952, 74, 521. (c) Brown, C. D., Chong J. M.; Shen, L. X. Tetrahedron 1999, 55, 14233.

J. Org. Chem, Vol. 67, No. 25, 2002 8897

Huang and Xie TABLE 4. Three-Component Reaction of Acetylenic Sulfones with Phenylselenomagnesium Bromide and Aliphatic Ketonesa

a The reaction was carried out at -20 °C by adding 1 (0.5 mmol), 2 (0.6 mmol), and 8 (0.5 mmol) simultaneously in THF/CH Cl (v/v 2 2 )1/4). b Isolated yield of purified Z-9 based on 1. The ratio of Z/E was determined by 400 MHz 1H NMR spectra of the unpurified reaction mixture.

TABLE 5. Reaction of Acetylenic Sulfones with Phenylselenomagnesium Bromide and r,β-Unsaturated Aliphatic Ketonesa

a A mixture of 1 (0.5 mmol), 2 (0.6 mmol), and 11 (0.5 mmol) in 5 mL of THF/CH Cl (1/4 v/v) was stirred at -20 °C. b Isolated yield 2 2 of purified Z-12 based on 1. The ratio of Z/E was determined by 400 MHz 1H NMR spectra of the unpurified reaction mixture.

removal of the solvent in vacuo, the crude product was purified with flash chromatography (silica/hexanes-ethyl acetate 10:1 v/v) and the desired adduct 1-phenyl-1-phenylseleno-2-(ptolylsulfonyl)ethene (4) was obtained. (Z)-1-Phenyl-1-phenylseleno-2-(p-tolylsulfonyl)ethene (Z-4): mp 132-134 °C; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J ) 8.2 Hz, 2H), 7.39 (d, J ) 8.0 Hz, 2H), 7.12-7.03 (m, 8H), 6.97 (t, J ) 7.5 Hz, 2H), 6.76 (s, 1H), 2.48 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 155.7, 143.9, 137.9, 137.3, 135.3, 129.2, 128.3, 128.1, 128.0, 127.64, 127.6, 127.2, 127.1, 21.1; IR (KBr) 1595, 1320, 1142 cm-1; MS (EI) m/z (%) 414 (24.7, M+), 257 (15.1, M+ - PhSe), 102 (13.6, M+ - PhSe - SO2Tol), 91 (100, C6H5CH2+). Anal. Calcd for C21H18O2SSe: C, 61.02; H, 4.39. Found: C, 61.02; H, 4.37.

8898 J. Org. Chem., Vol. 67, No. 25, 2002

(E)-1-Phenyl-1-phenylseleno-2-(p-tolylsulfonyl)ethene (E-4): mp 149 °C (lit.2b mp 152 °C); 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J ) 7.2 Hz, 2H), 7.44-7.38 (m, 3H), 7.32-7.24 (m, 5H), 7.19 (d, J ) 8.0 Hz, 2H), 7.10 (d, J ) 8.0 Hz, 2H), 6.16 (s, 1H), 2.36 (s, 3H); IR (KBr) 1594, 1321, 1142 cm-1; MS (EI) m/z (%) 414 (23.4, M+), 257 (18.6, M+ - PhSe), 102(8.6, M+ - PhSe - SO2Tol,), 91 (100, C6H5CH2+). The Tandem Reaction of Phenylselenomagnesium Bromide with Acetylenic Sulfones and Aldehydes. Preparation of 6. General Procedure. To a colorless solution of phenylselenomagnesium bromide (0.6 mmol) in THF/CH2Cl2 (v/v ) 1:4, 5 mL), prepared in situ from phenylmagnesium bromide and powder selenium, were added acetylenic sulfone (0.5 mmol) and aldehyde (0.5 mmol) at -20 °C with stirring.

Three-Component Conjugate-Nucleophilic Addition TABLE 6. Reaction of Acetylenic Sulfones with Phenylselenomagnesium Bromide and r,β-Unsaturated Aromatic Ketonesa

entry

R1

R2

Ar

time (h)

yield of Z-14 (%) (Z/E)b

1 2 3 4 5 6 7

Ph Ph Ph Ph Ph n-C5H11 n-C5H11

Ph Ph p-CH3OC6H4 p-ClC6H4 CH3 Ph Ph

Ph p-CH3OC6H4 Ph p-CH3C6H4 Ph p-CH3OC6H4 Ph

4.5 4 4 3.5 3 3.5 3.5

63 (Z-14a, >95/5) 69 (Z-14b, >96/4) 68 (Z-14c, >95/5) 57 (Z-14d, >96/4) 55 (Z-14e, >96/4) 70 (Z-14f, 96/4) 57 (Z-14g, >95/5)

a Mixture of 1 (0.5 mmol), 2 (0.6 mmol), and 13 (0.5 mmol) in 5 mL of THF/CH Cl (1/4 v/v) was stirred at -20 °C. b Isolated yield of 2 2 purified Z-14 based on 1. The ratio of Z/E was determined by 400 MHz 1H NMR spectra of the unpurified reaction mixture.

SCHEME 5

The reaction mixture turned to a pale yellow solution, which was maintained stirring at -20 °C for 50-90 min. After the reaction was complete (monitored by TLC), the reaction was quenched with saturated NH4Cl and extracted with CH2Cl2. The organic phase was washed with saturated brine and dried over MgSO4. After filtration and removal of the solvent in vacuo, the crude product was purified with flash chromatography (silica/hexanes-ethyl acetate 8:1 v/ v) and the desired tandem adduct 6 was obtained. (Z)-3-Phenyl-3-phenylseleno2-(p-tolylsulfonyl)-1-(p-nitrophenyl)-2-propen-1-ol (Z-6a): mp 180-181°C; 1H NMR (400 MHz, CDCl3) δ 7.98 (d, J ) 8.8 Hz, 2H), 7.79 (d, J ) 8.3 Hz, 2H), 7.34 (d, J ) 8.2 Hz, 2H), 7.23 (d, J ) 8.0 Hz, 2H), 7.12-7.08 (m, 1H), 7.02-6.93 (m, 8H), 6.82 (s, 1H), 5.56 (d, J ) 11.0 Hz, 1H), 4.32 (d, J ) 11.1 Hz, 1H), 2.44 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.2, 148.4, 146.9, 144.9, 138.0, 137.0, 136.8, 136.2, 129.3, 128.8, 128.5, 128.2, 127.8, 127.7, 126.5, 123.1, 73.1, 21.6; IR (KBr) 3478, 1517, 1343, 1260, 1134 cm-1; MS (EI) m/z (%) 408 (24.0, M+ - PhSe), 252 (59.2, M+ - PhSeH - SO2Tol), 91 (100, C6H5CH2+). Anal. Calcd for C28H23NO5SSe: C, 59.58; H, 4.11; N, 2.48. Found: C, 59.40; H, 4.25; N, 2.52. The Three-Component Reaction of Phenylselenomagnesium Bromide with Acetylenic Sulfones and Ketones. Preparation of 9, 12, or 14. General Procedure. To a colorless solution of phenylselenomagnesium bromide (0.6 mmol) in THF/CH2Cl2 (v/v ) 1:4, 5 mL) were added acetylenic sulfone (0.5 mmol) and ketone (0.5 mmol) at -20 °C with stirring. The reaction mixture turned to a pale yellow solution, which was maintained stirring at -20 °C for 2.5-5 h. After usual workup, the desired tandem adduct 9, 12, or 14 was obtained. (Z)-3-Methyl-2-(p-tolylsulfonyl)-1-phenyl-1-phenylseleno-1-hexen-3-ol (Z-9a): mp 121-123 °C; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J ) 8.3 Hz, 2H), 7.38 (d, J ) 8.0 Hz, 2H), 7.07 (t, J ) 7.6 Hz, 1H), 6.93-6.81 (m, 7H), 6.75 (s, 1H), 6.64 (d, J ) 6.34 Hz, 1H), 4.48 (br, 1H), 2.48 (s, 3H), 1.47-

1.42 (m, 2H), 1.26-1.18 (m, 2H), 1.12 (s, 3H), 0.72 (t, J ) 7.26 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 152.8, 143.8, 142.1, 139.4, 137.6, 137.5, 129.6, 129.1, 128.5, 128.4, 128.1, 127.7, 127.6, 127.3, 127.0, 126.7, 78.4, 45.1, 30.8, 21.7, 17.0, 13.9; IR (KBr) 3549, 1276, 1139 cm-1; MS (EI) m/z (%) 343 (14.1, M+ - PhSe,), 187 (13.9, M+ - PhSeH - SO2Tol), 91 (100, PhCH2+). Anal. Calcd for C26H28O3SSe: C, 62.52; H, 5.65. Found: C, 62.39; H, 5.92. (Z)-3-(p-Nitrostyryl)-2-(p-tolylsulfonyl)-1-phenyl-1-phenylseleno-1-buten-3-ol (Z-12a): mp 136-138 °C; 1H NMR (400 MHz, CDCl3) δ 8.17 (d, J ) 8.3 Hz, 2H), 8.04 (d, J ) 8.8 Hz, 2H), 7.41 (d, J ) 8.0 Hz, 2H), 7.12 (d, J ) 8.8 Hz, 2H), 7.03-6.99 (m, 2H), 6.86-6.82 (m, 3H), 6.75-6.69 (m, 3H), 6.58 (t, J ) 7.5 Hz, 1H), 6.45 (d, J ) 8.5 Hz, 1H), 6.33 (d, J ) 16.0 Hz, 1H), 5.96 (d, J ) 16.0 Hz, 1H), 5.12 (s, 1H), 2.51 (s, 3H), 1.59 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 154.3, 146.2, 143.7, 142.6, 141.1, 139.2, 138.4, 137.0, 136.6, 128.7, 128.4, 128.3, 128.1, 127.7, 127.4, 127.3, 127.2, 126.8, 126.5, 126.4, 124.5, 123.0, 76.3, 30.1, 21.2; IR (KBr) 3460, 1516, 1341, 1281, 1134 cm-1; MS (EI) m/z (%) 448 (3.12, M+ - PhSe), 292 (20.33, M+ - PhSeH - SO2Tol), 91 (100, PhCH2+). Anal. Calcd for C31H27NO5SSe: C, 61.59; H, 4.50; N, 2.31. Found: C, 61.32; H, 4.81; N, 2.42. (Z)-1,3,5-Triphenyl-4-(p-tolylsulfonyl)-5-phenylseleno4-penten-1-one (Z-14a): mp 150-151 °C; 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J ) 8.4 Hz, 2H), 7.59-7.53 (m, 3H), 7.437.39 (m, 2H), 7.11-7.0 (m, 8H), 6.94-6.90 (m, 7H), 6.75-6.67 (br, 2H), 4.84 (dd, J ) 9.7 Hz, 3.9 Hz, 1H), 4.37-4.30 (m, 1H), 3.40 (dd, J ) 18.1 Hz, 3.9 Hz, 1H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 196.7, 154.5, 143.9, 139.7, 139.1, 138.6, 137.5, 137.4, 136.6, 133.0, 129.1, 128.9, 128.5, 128.4, 128.3, 128.2, 128.0, 127.9, 127.8, 127.7, 127.3, 126.2, 43.1, 41.4, 21.5; IR (KBr) 1685, 1301, 1141 cm-1; MS (EI) m/z (%) 465 (8.0, M+ PhSe), 309 (12.1, M+ - PhSeH - SO2Tol), 105 (100, PhCO+). Anal. Calcd for C36H30O3SSe: C, 69.56; H, 4.86. Found: C, 69.40; H, 4.98.

J. Org. Chem, Vol. 67, No. 25, 2002 8899

Huang and Xie

Acknowledgment. This work was supported by project 29772007 of the National Natural Science Foundation of China and the Doctoral Foundation of the National Education Ministry of China. Supporting Information Available: 1H, and 13C NMR spectra for compounds Z-6a-t, 9a-e, 12a-f, 14a-g, E-6c,

8900 J. Org. Chem., Vol. 67, No. 25, 2002

and Z-4, E-4. Experimental details, elemental analysis, and spectral data for all new compounds not described within the text, as well as the ORTEP figures of compounds Z-4 and Z-6f. This material is available free of charge via the Internet at http://pubs.acs.org. JO026249B